WO2005086254A1 - Transistor à effet de champ, procédé de fabrication de celui-ci est procédé de fabrication d'un élément stratifié - Google Patents

Transistor à effet de champ, procédé de fabrication de celui-ci est procédé de fabrication d'un élément stratifié Download PDF

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Publication number
WO2005086254A1
WO2005086254A1 PCT/JP2005/004586 JP2005004586W WO2005086254A1 WO 2005086254 A1 WO2005086254 A1 WO 2005086254A1 JP 2005004586 W JP2005004586 W JP 2005004586W WO 2005086254 A1 WO2005086254 A1 WO 2005086254A1
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Prior art keywords
organic semiconductor
field effect
effect transistor
producing
layer
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PCT/JP2005/004586
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English (en)
Inventor
Daisuke Miura
Tomonari Nakayama
Toshinobu Ohnishi
Makoto Kubota
Akane Masumoto
Hidetoshi Tsuzuki
Makiko Miyachi
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Canon Kabushiki Kaisha
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Priority to US10/555,614 priority Critical patent/US7491967B2/en
Publication of WO2005086254A1 publication Critical patent/WO2005086254A1/fr
Priority to US12/354,745 priority patent/US8021915B2/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure
    • H10K10/476—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure comprising at least one organic layer and at least one inorganic layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine

Definitions

  • the present invention relates to a field effect transistor, a method of producing the field effect transistor, and a method of producing a laminated member.
  • H05-55568 phthalocyanines including lead phthalocyanine, low-molecular weight compounds such as perylene and tetracarboxylic acid derivatives thereof disclosed in Japanese Patent Application Laid-Open No. H05-190877; aromatic oligomers typified by thiophene hexamers called ⁇ - thienyl or sexthiophene and high molecular compounds such as polythiophene, polythienylenevinylene, and poly-p-phenylene vinylene disclosed in Japanese Patent Application Laid-Open No. H05-190877. Most of those compounds are described in Advanced Material, 2002, vol. 2, p. 99-117.
  • a compound with an extended ⁇ conjugated system is typically insoluble or hardly soluble in a solvent.
  • a pentacene thin film is produced by means of vacuum vapor deposition because pentacene has high crystallinity and is insoluble in a solvent.
  • the pentacene thin film produced by means of vacuum vapor deposition is known to exhibit a high field effect mobility, but involves a problem in that the pentacene thin film is unstable in the air, is susceptible to oxidation, and is thus apt to deteriorate .
  • an organic semiconductor using as an organic semiconductor film a ⁇ conjugated system polymer is excellent in processability.
  • the organic semiconductor can easily be formed into a thin film by means of solution coating or the like. Therefore, the applied development of the organic semico d ⁇ ctor has been pursued ("Japanese Journal of Applied Physics", The Japan Society of Applied Physics, 1991, vol. 30, p. 596-598).
  • the arrangement state of molecular chains is known to largely affect the electrical conductivity of the ⁇ conjugated system polymer.
  • the field .effect mobility of a ⁇ conjugated system polymer field effect transistor greatly depends on the arrangement state of molecular chains in a semiconductor layer ("Nature", Nature Publishing Group, 1999, vol.
  • the arrangement of molecular chains in the ⁇ conjugated system polymer is performed during the period from the application of a solution to the drying of the solution, so the arrangement state of the molecular chains may vary to a large extent owing to a change in environment and a difference in application method.
  • an FET has been reported, which uses a film obtained by: forming a thin film of a soluble precursor of pentacene by application; and transforming the precursor into pentacene through heat treatment (J. Appl . Phys., vol. 79, 1996, p. 2136) .
  • a semiconductor layer having crystallinity and orientation has been formed by undergoing a process such as vacuum film formation.
  • a process such as vacuum film formation.
  • an acene is a representative example of the organic semiconductor compound.
  • the acene is susceptible to oxidation, and is thus apt to deteriorate.
  • a film obtained by a simple method using application method faces the task of establishing an approach to forming a film excellent in both of orientation and crystallinity.
  • the present invention has been made in order to solve the above problems, and an object of the present invention is to provide a field effect transistor which enables an organic semiconductor layer having high crystallinity and high orientation to be formed and which exhibits a high field effect mobility. Another object of the present invention is to provide a method of producing a field effect transistor which enables the above field effect transistor to be easily obtained.
  • a field effect transistor having an organic semiconductor layer, including: an organic semiconductor layer containing at least porphyrin; and a layer composed of at least a polysiloxane compound, the layer being laminated on the organic semiconductor layer so as to be in intimate contact with the organic semiconductor layer,
  • the term "porphyrin” in the description including the claims in the specification is a concept comprehending a wide variety of porphyrins, and means a compound having a porphyrin skeleton.
  • the term “porphyrin” is a concept also comprehending metal porphyrin derivatives such as a tetrabenzoporphyrin copper complex.
  • polysiloxane compound means a compound having multiple siloxane bonds, and is a concept .comprehending an organopolysiloxane, a polysilsexyoxane, and the like.
  • those layers may contain other compounds as long as the functions of the compounds of the layers are not impaired.
  • the polysiloxane compound is represented by the following general formula (1) : General formula (1)
  • R x to R 4 each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, or a siloxane unit. R x to R 4 may be identical to or different from one another, n represents an integer of 1 or more.
  • the polysiloxane compound is a polysilsesquioxane compound represented by the following general formula (2) and/or the following general formula (6) :
  • R 7 to Rio each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 7 to R 10 may be identical to or different from one another, m and n each represent an integer of 0 or more, and the sum of m and n is an integer of 1 or more.
  • a copolymerization form may be random copolymerization or block copolymerization .
  • General formula ( 6 ) General formula ( 6 ) :
  • R 2i to R 24 each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 21 to R 24 may be identical to or different from one another, o and p each represent an integer of 0 or more, and the sum of o and p is an integer of 1 or more.
  • a copolymerization form may be random copolymerization or block copolymerizatiqn. ) .
  • the porphyrin is represented by the following general formula (3) : General formula (3)
  • Ru ' s represent at least one kind selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl, oxyalkyl, thioalkyl, or alkylester group having 1 to 12 carbon atoms, and Rn's may be identical to or different from one another.
  • adjacent Rn's may form an aromatic ring which may have a substituent.
  • the adjacent Rn's may be connected to a porphyrin ring which may have a substituent through the formed aromatic ring.
  • R ⁇ 2 's represent at least one kind selected from the group consisting of a hydrogen atom and an aryl group which may have a substituent.
  • R ⁇ 2 ' s may be identical to or different from one another.
  • X represents a hydrogen atom or a metal atom.) .
  • at least one pair of the adjacent Rn's in the general formula (3) forms an aromatic ring.
  • the aromatic ring formed by the at least one pair of the adjacent Rn's in the general formula (3) is obtained by heating a precursor having a bicyclo [2.2.2] octadiene skeleton structure which may have a substituent.
  • Bragg angles (2 ⁇ ) of CuKc In further aspect of the field effect transistor, Bragg angles (2 ⁇ ) of CuKc.
  • X-ray diffraction in the organic semiconductor layer have peaks at 8.3° ⁇ 0.2°, 10.1° ⁇ 0.2°, 11.8° + 0.2°, and 14 . 4 ° ⁇ 0 . 2 ° .
  • X-ray diffraction in the organic semiconductor layer have peaks at 8.4° ⁇ 0.2°, 11.9° + 0.2°, and 16.9° ⁇ 0.2°.
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer have peaks at 7.2° ⁇ 0.2°, 7.8° ⁇ 0.2 11.7° ⁇ 0.2°, and 23.5° ⁇ 0.2° .
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer have peaks at 7.3° ⁇ 0.2°, 7..8° ⁇ 0.2°, 11.7° ⁇ 0.2°, and 19.6° ⁇ 0.2° .
  • a method of producing a field effect transistor having an organic semiconductor layer including the step of laminating an organic semiconductor layer containing at least porphyrin and a layer composed of at least a polysiloxane compound in such a manner that the layers are in intimate contact with each other.
  • the polysilo-xane compound is represented by the general formul-a (1) .
  • the polysiloxane compound is a polysiloxane compound represented by the general formula (2) and/or the general formula (6) .
  • the porphyrin is represented by the general formula (3) .
  • at least one pair of the adjacent Rn's in the general formula (3) forms an aromatic ring.
  • the aromatic ring formed by the at least one pair of the adjacent Rn's in the general formula (3) is obtained by heating a precursor having a bicyclo[2.2.2] octadiene skeleton structure which may have a substituent.
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer form peaks at 8.3° ⁇ 0.2°, 10.1° ⁇ 0.2°, 11.8° ⁇ 0.2°, and 14.4° ⁇ 0.2°.
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer form peaks at 8.4° ⁇ 0.2°, 11.9° ⁇ 0.2% and 16.9° ⁇ 0.2°.
  • the method of producing a field effect transistor having an Organic semiconductor layer is further aspect of the method of producing a field effect transistor having an Organic semiconductor layer,.
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer form peaks at 7.2° ⁇ 0.2°, 7.8° + 0.2°, 11.7° ⁇ 0.2°, and 23.5° ⁇ 0.2° .
  • Bragg angles (2 ⁇ ) of CuK ⁇ X-ray diffraction in the organic semiconductor layer form peaks at 7.3° ⁇ 0.2°, 7.8° ⁇ 0.2°, 11.7° ⁇ 0.2°, and 19.6° ⁇ 0.2°.
  • a method of producing a laminated member having an organic semiconductor layer including at least the steps of: providing a crystallization promoting layer on a substrate; providing an organic semiconductor precursor on the crystallization promoting layer; and applying energy to the organic semiconductor precursor to form a layer composed of an organic semiconductor.
  • the crystallization promoting layer has a function of promoting bonding between crystal grains .
  • the energy is light energy or heat energy.
  • the step of applying energy to the organic semiconductor precursor to form a. layer composed of an organic semiconductor includes a step of allowing the organic semiconductor precursor to cause an elimination reaction.
  • the elimination reaction is a retro Diels-Alder reaction.
  • the energy is continuously applied even after completion of the elimination reaction.
  • the step of providing the organic semiconductor precursor is a step of applying or printing a solution containing the organic semiconductor precursor.
  • the crystallization promoting layer contains a polysiloxane compound.
  • a field effect transistor having an organic semiconductor layer, including at least: a substrate; a crystallization promoting layer on the substrate; and the organic semiconductor layer in contact with the crystallization promoting layer.
  • Figs. IA and IB are schematic sectional drawings each showing part of an embodiment of a field effect transistor , of the present invention.
  • Fig. 2 is a schematic sectional drawing showing part of a field effect transistor according to Example 4 of the present invention.
  • Fig. 3 is a drawing showing electrical characteristics of a field effect transistor obtained in Example 5 of the present invention.
  • Fig. 4 is an X-ray diffraction pattern on a transistor substrate obtained in Example 3 of the present invention.
  • Fig. 5 is an X-ray diffraction pattern on a transistor substrate obtained in Example 5 of the present invention.
  • Fig. 6 is an X-ray diffraction pattern on a transistor substrate obtained in Example 6 of the present invention .
  • FIG. 7 is an X-ray diffraction pattern on a transistor substrate obtained in Example 7 of the present invention .
  • Fig. 8 is a schematic sectional drawing showing a field effect transistor of Example 12 of the present invention .
  • Fig. 9 is an X-ray diffraction pattern of a transistor substrate obtained in Example 13 of the present invention .
  • a field effect transistor is a device having at least an organic semiconductor, an insulator, and a conductor.
  • the insulator is an insulating film (layer) for covering the conductor serving as an electrode.
  • the organic semiconductor is an organic semiconductor layer that responds to a stimulus (electric field) generated by such a conductor (electrode) .
  • the organic semiconductor layer is a layer the electrical characteristics of which change with an electric field. More specifically, the organic semiconductor layer is a layer the conductivity of which, that is, the amount of a current passing through the organic semiconductor layer, changes with a change in electric field.
  • IA is a schematic sectional drawing showing the field effect transistor according to this embodiment.
  • Reference numeral 8 denotes a substrate; 1, a gate electrode; 2, a gate insulating layer; 4, a source electrode; 5, a drain electrode; 6, an organic semiconductor layer; and 7, a sealing layer.
  • the gate electrode 1 is placed on the surface of the substrate 8
  • the gate insulating layer 2 is placed on the gate electrode 1
  • the source electrode 4 and the drain electrode 5 are placed on the surface of the insulating layer 3 so as to be separated from each other.
  • the organic semiconductor layer 6 is placed on the source electrode 4, the drain electrode 5, and the insulating layer 2 serving as a separation region between the electrodes, so as to be in contact with both the electrodes 4 and 5.
  • the insulating layer 2 is placed to cover the gate electrode 1. Furthermore, the organic semiconductor layer 6 is covered with the sealing layer 7. The substrate 8 and the sealing layer 7 may be interchanged with each other.
  • a voltage is applied to the gate electrode 1
  • a positive or negative charge is induced at an interface between the gate insulating layer 2 and the organic semiconductor layer 6.
  • a voltage is applied between the source electrode 4 and the drain electrode 5
  • a charge moves between both the electrodes, thereby generating a current.
  • a charge is uniformly generated at the interface between the gate insulating layer 2 and the organic semiconductor layer 6 when a voltage is applied to the gate electrode 1, and further, a charge moves efficiently with little barrier when a voltage is applied between the source electrode 4 and the drain electrode 5, making the transistor exhibit a high field effect mobility.
  • the inventors of the present invention have made extensive studies to find a method of forming an organic semiconductor layer interface which allows a charge to be uniformly generated and which allows the generated charge to move efficiently. As a result, the inventors have found that, by laminating a specific organic semiconductor material and a layer promoting crystallization (crystallization promoting layer) with an interface at which a charge moves (the interface between the gate insulating layer 2 and the organic semiconductor layer 6 in Fig.
  • the field effect transistor of the present invention is a field effect transistor having an organic semiconductor layer, wh-erein the organic semiconductor layer containing at least porphyrin and a layer composed of at least a jolysiloxane compound are preferably laminated so as to be in intimate contact with each other.
  • the terra "intimate contact” means the state where the organic semiconductor layer is in contact with the layer composed at least a polysiloxane compound via no other layer.
  • a field effect transistor having a layer composed of a polysiloxane compound (hereinafter, referred to as an A layer) and an organic semiconductor layer having porphyrin (hereinafter, referred to as a ⁇ B layer) being laminated so as to be in intimate contact with ' each other in part of or the entire surface of the device is preferable because the field effect transistor exhibits a high field effect mohility.
  • an A layer a polysiloxane compound
  • a ⁇ B layer organic semiconductor layer having porphyrin
  • any other crystallization promoting layers having a funct ion of promoting crystallization can be used ins tead of the A layer, and an organic semiconductor layer the crystallization of which is promoted by the crystallization promoting layer can be used instead of the B layer.
  • a base structure on which the crystallization promoting layer is formed (the structure is generally a structure composed of a substrate, a gate electrode, and a gate insulating layer; but the gate insulating layer can be omitted in some cases, the structure can be composed only of the substrate depending on a lamination order, or other layers may be formed in the structure) may be referred to as a substrate.
  • the term “function of promoting crystallization” refers to a function of promoting stabilization of crystal grains (which may involve the movement and rotation of the crystal grains) and/or bonding between the crystal grains.
  • the term “crystallization promoting layer” refers to a layer promoting stabilization of crystal grains (which may involve the movement and rotation of the crystal grains) and/or bonding between the crystal grains.
  • the B layer is formed on the A layer.
  • the present invention is not limited thereto although it is preferable to form the B layer on the A layer from the viewpoint of imparting an influence of the A layer during the formation of the B layer.
  • a polysiloxane compound of the present invention is a polymer having a siloxane structure (- Si-O-) and an organic silane structure.
  • the compound may be a copolymer with another organic or inorganic high molecular compound.
  • each of the siloxane structure and the organic silane structure may be introduced into a main c ain or may be grafted to a side chain. Crystallization is promoted because the organic semiconductor layer as the B layer hardly receives a constraint from the A- layer during crystallization by virtue of the effect of combination of the siloxane stracture (-Si-O-) and the organic silane structure.
  • the polysiloxane compound of the present invention may be linear or cyclic, but preferably has a high order cross-linked or bra_nched structure.
  • high order cross-linked or branched structure includes a network structure, a ladder-like structure, a basket-like structure, a star—like structure, and a dendritic structure.
  • the cross- linked or branched structure is not necessarily formed through a siloxane structure.
  • the structure may contain a structure in which organic groups such as a vinyl group, an acryloyl group, an epoxy group, and a cinnamoyl group are cross-linked or a structure branched through an organic group which is trifunctional or more.
  • a layer of the polysiloxane compound of the present invention has a high order cross-linked or branched structure.
  • the layer of the polysiloxane compound allows an amorphous layer to be formed on a wide area irrespective of the state and shape of the substrate surface.
  • the interface between the A layer and the B layer is uniform.
  • the polysiloxane compound to be used for the A layer of the present invention has, for example, a structure represented by the following general formula (1), and its main chain is a siloxane unit and any one of its side chains is a substituent having an organic group such as a hydrogen atom or a carbon atom.
  • general formula (1) a structure represented by the following general formula (1), and its main chain is a siloxane unit and any one of its side chains is a substituent having an organic group such as a hydrogen atom or a carbon atom.
  • Ri to R 4 each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, or a siloxane unit.
  • R x to R 4 may be identical to or different from one another, n represents an integer of 1 or more.
  • the substituents Ri to R 4 may be the siloxane units such as those shown below.
  • R's each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, a substituted or unsubstituted phenyl group, or a siloxane unit shown above. R's may be the same functional group or may be different functional groups .
  • the shape of the polysiloxane a ⁇ y be of a linear structure, a cyclic structure, a network structure, a ladder-like structure, a basket-like structure, or the like, depending on the kinds of substituents in the formula (1) .
  • the ⁇ polysiloxane to be used in the present invention may b»e of any of the structures.
  • polysiloxane compound to be used for the A layer irx is a polysiloxane compound having at least a specific silsesquioxane skeleton represented by the following general formula (2) and/or a specific organosiloxane skeleton represented by the following general formula (6) :
  • general formula (2) a specific silsesquioxane skeleton represented by the following general formula (2) and/or a specific organosiloxane skeleton represented by the following general formula (6) :
  • R 7 to Rio each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R to Rio may be identical to or different from one another, m and n each represent an integer of 0 or more, and the sum of m and n is an integer of 1 or more.
  • a copolymerization form may be random copolymerization or block copolymerization.
  • R 21 to R 24 each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 2i to R 24 may be identical to or different from one another, o and p each represent an integer of 0 or more, and the sum of o and p is an integer of 1 or more.
  • a copolymerization form may be random copolymerization or block copolymerization.
  • the polysiloxane compound may contain one or both of the silsesquioxane skeleton represented by the general formula (2) and the organosiloxane skeleton represented by the general formula (6).
  • substituents R 7 to Rio and Ru to R 14 having carbon atoms corresponding to the side chains of the silsesquioxane skeleton and the organosiloxane skeleton each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group, and they may be the same functional group or may be different functional gr oups depending on sites.
  • Examples of such a functiona-1 group include: an unsubstituted alkyl group such as a methyl group or an ethyl group; an unsubstituted phenyl group; and a substituted phenyl group such as a dimethylphenyl group or a naphthyl group.
  • the substituents R 7 to R 10 may contain various atoms such as an oxygen atom, a nitrogen atom, and- a metal atom as well as a carbon atom and a hydrogen- atom.
  • the silsesquioxane s-keleton of the compound used in the present invention will be described.
  • the general formula (2) rep-resents a structural formula having a structure in which m silsesquioxane units (hereinafter, referred to as first units) each having the substituen-ts R 7 and R 8 are repeated and a structure in which ri silsesquioxane units (hereinafter, referred to as second units) each having the substituents R 9 and Rio are repeated are connected (m and n each represent an integer of 0 or more, and m + n represents an integer of 1 or more) .
  • the formula does not mean that the repeated first units and the repeated second units are separated. Both the units may be s eparately connected or may be connected whil e being intermingled at random.
  • the general formula (2) represents a structural formula having a structure in which o diorganosiloxane units (hereinaft r, referred to as first units) each having the substituents Ru and R ⁇ 2 are repeated and a structure in which 1 diorganosiloxane units (hereinafter, referred to as second units) each having the substituents R 13 and R i4 are repeated are connected (o and 1 each represent an integer of 0 or more, and o + 1 represents an integer of 1 or more) .
  • the formula does not mean that the repeated first units and the repea-ted second units are separated. Both the units may be separately connected or may be connected while being intermingled at random.
  • Examples of a method of forming the A layer in the present invention mainly containing a polysiloxane compound having the silsesquioxane skeleton and/or the organosiloxane skeleton represented by the general formulae (2) and (6) include: a method involving applying a solution containing a polyorganosilsesquio-cane compound represented by at least one of the following general formulae (4) and (5) and/or a polyorganosiloxane compound represented by at least one of the following general formulae (7) and (8) onto a substrate and drying the applied solution under heating; and a method involving applying a sol obtained by hydrolyzing a silicon monomer onto a substrate and drying the applied sol under heating.
  • the heating causes the terminals of the compound to be condensed through a dehydration or dealcoholization reaction.
  • the polyorganosilsesquioxane compound is connected in a ladder structure, while the polyorganosiloxane compound is increased in molecular weight and densified.
  • the drying temperature is not high enough for the organic matter to completely disappear. Therefore, the raw material compounds do not have a complete .
  • a trifunctional organic silicon monomer and/or a bifunctional organic silicon monome r each having an organic group R is/are hydrolyzed in a solvent such as alcohol to produce a silanol compound.
  • the silicon monomer shown in the above reaction formulae is an alkoxide from which R"OH is eliminated by hydrolysis.
  • the silicon monomer may also be a chloride, however, in this case, hydrogen chloride is generated as an eliminated component.
  • the silanol compound obtained by hydrolysis is further subjected-, to dehydration condensation through heating or the like to produce a polyorganosilsesquioxane compound and a polyorganosiloxane compound.
  • R 7 and R 8 each represent a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 7 and R 3 may be the same functional group.
  • R ⁇ 3 to R ⁇ 6 each represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, z represents an integer of 1 or more.
  • R 9 and Rio each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 9 and R ⁇ 0 may be the same functional group.
  • R i to R 20 each represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, y represents an integer of 1 or more.
  • R 25 and R 2 e each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 25 and R 26 may be the same functional group.
  • R 27 and R 28 each represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, q represents an integer of 1 or more.
  • R 2 g and R 3 o each represent a substituted or unsubstituted alkyl or alkenyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted phenyl group.
  • R 29 and R 30 may be the same functional group.
  • R 3 ⁇ and R 32 each represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom, r represents an integer of 1 or more.).
  • a small amount of an acid such as formic acid may be added to the application solution for the purpose of aiding a reaction in which silsesquioxane compounds serving as oligomers mutually cross-link during the drying step.
  • the addition amount of an acid is not particularly limited, a cross-linking reaction is promoted when formic acid is added in an amount in the range of 1 wt% to 30 wt% with respect to the solid weight ' of the polyorganosilsesquioxane compound in the application solution.
  • An addition amount of less 1 wt% provides an insufficient promoting effect on the cross-linking reaction, while an addition amount in excess of 30 wt% may inhibit the film formation after the drying.
  • the trifunctional silicon monomer and/or the bifunctional silicon monomer shown in the reaction formulae (11) and (12) is/are stirred in a solvent in the coexistence of water and a catalyst at room temperature or under heating, whereby sol is prepared through hydrolysis and dehydration condensation reactions similar to those in the reaction formulae (11) and (12) . Heating of the applied film of the resultant sol leads to condensation of silanol and an unreacted alkoxide through a dehydration or dealcoholization reaction. Thus, a dense silsesquioxane or organosiloxane skeleton such as one represented by the general formula (2) or (6) is formed.
  • a silicon monomer that can be used for preparing sol include: a trifunctional silicon monomer such as methyltrimethoxysilane, methyltriethoxysilane, ethyItrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, vinyltrimethoxysilane, 3- aminopropyltriethoxysilane, or phenyltrimethoxysilane; and a bifunctional silicon monomer such as dimethyldimethoxysilane or diphenyldimethoxysilane .
  • water and a catalyst can be added to promote the hydrolysis of a monomer.
  • the addition amount of water is in the range of 0.1 to 20 equivalents with respect to OR" groups in the monomer in the reaction formula (11) or (12) .
  • an acid catalyst or a basic catalyst can be used for the catalyst.
  • an available acid catalyst include hydrochloric acid, nitric acid, p- toluenesulfonic acid., trifluoromethanesulfonic acid, acetic acid, formic acid, trifluoroacetic acid and alkylphosphoric acid. Of those, formic acid is more preferable because it is lowly corrosive, and vaporizes during the drying of the applied film under heating so that it does not remain in the film.
  • an available basic catalyst examples include sodium hydroxide, potassium hydroxide, and tetramethylammonium hydroxide. Of those, tetramethylammonium hydroxide is preferable because the remaining of an alkali metal such as sodium is responsible for the deterioration of the electrical characteristics of the device.
  • the addition amount of a catalyst is in the range of 1 wt% to 30 wt% with respect to the solid weight of the silicon monomer in the solution. An addition amount of less 1 wt% provides an insufficient promoting effect on the cross-linking reaction, while an addition amount in excess of 30 wt% may deteriorate the film properties after the drying.
  • the polyorganosilsesquioxane compounds shown in the general formulae (4) and C5), the polyorganosiloxane compounds shown in the general formulae (7) and (8), and the silicon monomer in the reaction formula (11) or (12) can be mixed for use.
  • water and a catalyst can be added as in the preparation of sol.
  • the addition amount of water is in the range of 0.1 to 20 equivalents with respect to OR" groups in the monomer.
  • the addition amount of a catalyst is in the range of 1 wt% to 30 wt% with respect to the solid weight of the mixtnre of a polyorganosilsesquioxane compound and/or a polyorganosiloxane compound and the silicon monomer.
  • a tetrafunctional silicon monomer such as tetramethoxysilane or tetraethoxysilane can be used in combination in order to enhance applicability and solvent resistance after the drying.
  • a heat treatment temperature is preferably 140°C or higher, more preferably in the range of 150°C to 230°C. Heating at a temperature lower than 140°C may result in an insufficient hydrolysis reaction.
  • a stabilizing agent that does not evaporate , vaporize, or burn out in the above-mentioned temperature range is removed from the solution system as much as possible during the processes of a cross- linking reaction and solvent removal.
  • An arbitrary solvent such as an alcohol or an ester can be used for the solvent of the application solution.
  • a method of applying a raw material solution for the A layer is not particularly limited, and the solution is applied by means of any one of the conventional coating methods such as a spin coating method, a cast method, a spray coating method, a doctor blade method, a die coating method, a dipping method, a printing method, an inkjet method, and a dropping method.
  • the spin coating method, the dipping method, the spray coating method, and the inkjet method are preferable because an application amount can be controlled so that a film having a desired thickness is formed. To keep the insulating properties of the resultant film, it is important to minimize the intrusion of dirt or the like in the application solution.
  • the A layer has a thickness of 10 nm or more, preferably in the range of 15 to 500 nm. This is because a thickness of less than 10 nm makes it difficult to obtain a uniform film.
  • the substrate Prior to the application of the A layer, the substrate may be subjected to surface modification for improving wettability such as ultrasonication in an alkali solution or irradiation with UV.
  • surface modification for improving wettability such as ultrasonication in an alkali solution or irradiation with UV.
  • the B layer preferably contains at least a porphyrin compound represented by the following general formula (3) .
  • Rn's represent at least one kind selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl, oxyalkyl, thioalkyl, or alkylester group having- 1 to 12 carbon atoms, and Rn's may be identical to or different from one another.
  • adjacent Rn's may form an aromatic ring which may have a substituent.
  • the adjacent Rn's may be connected to a porphyrin ring which may have a substituent through the formed aromatic ring.
  • R ⁇ 2 's represent at least one kind selected from the group consisting of a hydrogen atom and an aryl group which may have a substituent.
  • R ⁇ 2 ' s may be identical to or different from one another.
  • X represents a hydrogen atom or a metal atom. Examples of X include: various metals such as H, Cu, Zn, Ni, Co, Mg, and Fe; and atomic groups such as A1C1, TiO, FeCl, and SiCl 2 . Although X is not particularly limited, X particularly preferably represents a hydrogen atom or a copper atom. Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring .
  • Such a porphyrin compound can be formed into a film onto the substrate.on which the A layer is formed by means of a general approach such as a vacuum vapor deposition method or a dispersion application method.
  • a general approach such as a vacuum vapor deposition method or a dispersion application method.
  • examples of a porphyrin compound are shown. Unsubstituted and metal-free structures are mainly shown, but substituents, central metals, and central atomic groups are not limited. Of course, the compound of the present invention is not limited to those examples. 38
  • At least one pair of adjacent Rn's in the porphyrin compound represented by the general formula (3) preferably forms an aromatic ring.
  • the aromatic ring is more preferably one that can be obtained by heating an applied film obtained by solvent application of a precursor having a bicyclo [2.2.2] octadiene skeleton structure (hereinafter, referred to as a bicyclo body) because the crystallization of the porphyrin compound is promoted.
  • other energy applying means such as light irradiation can be used.
  • a reverse Diels-Alder reaction a retro Diels-Alder reaction
  • a preferable method of producing the B layer when a bicyclo body is used as a precursor involves: dissolving the bicyclo body into an organic solvent; applying the solution to the substrate on which the A layer is formed; and heating the applied solution to obtain a crystallized film of the porphyrin compound.
  • the A layer and the B layer have only to be in intimate contact with each other at least at portions of the layers, and another device component such as a partial electrode may be interposed between the A layer and the B layer.
  • the surface of the A layer may be subjected to modification by means of a general approach as required prior to the application of the B layer.
  • the organic solvent to be used into which the bicyclo compound is dissolved is not particularly limited as long as the bicylo compound does not cause a reaction or precipitate.
  • a mixture of two or more kinds of organic solvents may be used.
  • a halogen solvent is preferably used in consideration of the smoothness of the applied film surface and the uniformity of the film thickness.
  • the halogen solvent include chloroform, methylene chloride, dichloroethane, chlorobenzene, dichlorobenzene, trichlorobenzene, and 1,2- dichloroethylene .
  • the concentration of the solution which is arbitrarily adjusted in accordance with a desired thickness, is preferably in the range of 0.01 to 5 wt% .
  • a method of applying the B layer when a bicylo compound is used, along with that of applying the A layer, is not particularly limited, and the layer is applied by means' of any one of the conventional coating methods such as the spin coating method, the cast method, the spray coating method, the doctor blade method, the die coating method, the dipping method, the printing method, the inkjet method, and the dropping method.
  • the spin coating method, the dipping method, the spray coating method, and the inkjet method are preferable because an application amount can be controlled so that a film having a desired thickness is formed.
  • preliminary drying at 130°C or lower can be performed at the time of application of the bicyclo compound.
  • the applied and formed bicyclo skeleton is heated to cause a retro Diels-Alder reaction, with the result that the skeleton is transformed into an aromatic ring (benzo compound) in association with the elimination of an ethylene skeleton.
  • Crystal growth due to stacking of porphyrin rings occurs simultaneously with the production of the aromatic ring, so a crystallized film of the porphyrin compound is obtained.
  • an elimination reaction occurs at 140°C or higher.
  • a heating temperature for obtaining an increased field effect mobility is in the range of 150 to 280°C, preferably in the range of 170 to 230°C. .
  • a heating temperature of lower than 150°C does not result in the formation of a sufficient crystallized film, while a heating temperature in excess of 280°C results in the occurrence of cracks owing to abrupt film contraction.
  • the heating is performed on a hot plate, in an oven with internal air circulation, a vacuum oven, or the like, but a heating method is not limited.
  • a method involving heating instantaneously on a hot plate is preferable for obtaining uniform orientation.
  • rubbing treatment in which the applied film before the heating is lightly rubbed with cloth or the like can be performed in order to obtain improved crystallinity.
  • Examples of the cloth used for the rubbing treatment include, but not limited to, rayon, cotton, and silk.
  • examples of a bicyclo body are shown. Unsubstituted and metal-free structures are mainly shown, but substituents, the position at which the bicyclo ring in the molecule is present, central metals, and central atomic groups are not limited. Of course, the compound of the present invention is not limited to those examples. 48
  • the thickness of the B layer obtained through those operations is in the range of 10 to 200 nm, preferably in the range of 20 to 150 nm.
  • the thickness can be measured by means of a surface roughness measuring device, a level difference meter, or the like.
  • the B layer may be replaced with another general organic semiconductor compound such as phthalocyanine .
  • the organic film obtained in the present invention is most preferably used for a field effect transistor, but can be applied to other devices and the like.
  • Fig. IB is an enlarged schematic sectional drawing showing part of the field effect transistor of the present invention.
  • the field effect transistor of the present invention is composed of the gate electrode 1, the insulating layer 2, the A layer 3 (polysiloxane compound layer) , the source electrode 4, the drain electrode 5, and the B layer 6 (organic semiconductor layer) .
  • a substrate 8 is present on a side opposite to the insulating layer of the gate electrode 1.
  • the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are made of conductive materials.
  • the materials include: platinum, gold, silver, nickel, chromium, copper, iron, tin, antimonial lead, tantalum, indium, aluminum, zinc, magnesium, and alloys of those metals; conductive metal oxides such as an indium-tin oxide; and inorganic and organic semiconductors with increased conductivities through doping and the like such as a silicon single crystal, polysilicon, amorphous silicon, germanium, graphite, polyacetylene, polyparaphenylene, polythiophene, polypyrrol, polyaniline, polythienylenevinylene, and polyparaphenylenevinylene .
  • Examples of a method of producing an electrode include a sputtering method, a vapor deposition method, a printing method from a solution or a paste, an inkjet method, and a dip method.
  • an electrode material is preferably one out of the above materials that has small electrical resistance at a contact surface with the semiconductor layer.
  • the insulating layer may be any one as long as it allows the A layer to be uniformly applied, but is preferably one having a high dielectric constant and a low conductivity.
  • an insulating material for such a layer examples include: inorganic oxides and nitrides such as silicon oxide, silicon nitride, aluminum oxide, titanium oxide, and tantalum oxide; polyacrylate; polymethacrylate; polyethylene terephthalate; polyimide; polyether; polyamide; polyamideimide; polybenzoxazole; polybenzothiazole; phenol resins; polyvinylphenol; and epoxy resins.
  • the insulating materials one having high surface smoothness is preferable.
  • the A layer itself is excellent in insulating properties, the A layer may be adjusted to a thickness that allows the insulating properties to be expressed to serve as a gate insulating layer. The configuration in this case is the same as that shown in Fig.
  • the substrate 8 is present on the side opposite to the insulating layer of the gate electrode 1.
  • Fig. IB is the same as Fig. IA in this respect.
  • the substrate 8 that can be suitably used in the present invention include those obtained by processing silicon, glass,- metal, resin, and the like into plate, foil, film, and sheet shapes In particular, a resin substrate is preferable from the viewpoints of flexibility and processability.
  • Examples of a material to be used for the resin substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyetherimide (PEI), polyethersulfone (PES), polysulfone (PSF) , polyphenylene sulfide (PPS), polyetheretherketone (PEEK), polyallylate (PAR), polyamideimide (PAI), a polycycloolefin resin, an acrylic resin, polystyrene, ABS, polyethylene, polypropylene, a polyamide resin, a polycarbonate resin, a polyphenylene ether resin, and a cellulosic resin.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PI polyimide
  • PEI polyetherimide
  • PES polyethersulfone
  • PSF polysulfone
  • PPS polyphenylene sulfide
  • PEEK polyetheretherketone
  • PAR poly
  • the field effect transistor structure in the present invention may be of any one of a top contact electrode type, a bottom contact electrode type, and a top gate electrode type.
  • the structure is not limited to a horizontal type and may be of a vertical type.
  • a field effect transistor which is excellent in crystallinity and orientation, and which exhibits a high field effect mobility.
  • a method of producing a field effect transistor which enables the above field effect transistor to be easily obtained.
  • the field effect transistor of the present invention can be used for a plastic IC card, an information tag, a display, or the like because of its excellent crystallinity, excellent orientation, and high field effect mobility.
  • the step of heating a bicyclo precursor on the A layer to obtain the B layer probably plays an important role in allowing the A layer to function as a crystallization promoting layer for the B layer.
  • the bicyclo precursor is heated to cause an elimination reaction, a gap is observed to develop between crystal grains composed of the . resultant ' compound.
  • the organic semiconductor layer is not limited to a layer having a porphyrin compound (B layer) , and has only to be a layer which is composed of a compound involving the transformation from a precursor and the crystallization of which is promoted by the crystallization promoting layer.
  • a compound the molecular weight of which reduces owing to the transformation from a precursor is preferable as an organic semiconductor material in the organic semiconductor layer. More specifically, a layer containing pentacene obtained by eliminating a diazo group, a dicarbonyl group, and the like from a bicyclo body having these groups is also an organic semiconductor layer suitably used in the present invention.
  • an organic field effect transistor and a method of producing the same can be confirmed to be within the scope of the present invention as long as the following two points can be experimentally confirmed: one point is that at least one of the above-described movement, rotation, and bonding of crystal grains is promoted by the presence of a crystallization promoting layer in the step of forming an organic semiconductor layer and the other point is that a field effect mobility is increased by the presence of the crystallization promoting layer in the step.
  • the concept of the present invention is- useful not only in a method of producing a field effect transistor but also in methods of producing other organic devices, and, more widely, the whole methods of producing laminated bodies having organic semiconductor layers. All of those are included in the scope of the present invention.
  • Synthesis Examples and Examples are shown. However, the present invention is not limited to these examples.
  • Synthesis Example 1 (Step 1-1) A mixed solution of 3.16 g (39.5 mmol) of 1,3- cyclohexadiene, 10.5 g (34.1 mmol) of trans-1,2- bis (phenylsulfonyl) ethylene, and 200 ml of toluene was refluxed for 7 hours. After that, the solution was cooled and concentrated under reduced pressure to yield a reaction mixture.
  • Step 1-2 The reaction crude product was recrystallized ( chloroform/hexane) to yield 5,6- bis (phenylsulfonyl) -bicyclo [2.2.2] octa-2-ene (13.8 g, 35.6 mmol, 90% yield).
  • Step 1-2 The reaction system of a mixed solution of 7.76 g (20 mmol) of the resultant 5, 6-bis (phenylsulfonyl) - bicyclo [2.2.2] octa-2-ene and 50 ml of anhydrous tetrahydrofuran was replaced with nitrogen.
  • the dried product was purified by means of silica gel column chromatography (chloroform.) to yield ethyl-4,7- dihydro-4, 7-ethano-2H-isoindole-l-carboxylate (3.5 g, 16 mmol, 80% yield) .
  • Step 1-3 Under an argon atmosphere, a mixed solution of 0.42 g (1.92 mmol) of the resultant ethyl-4,7- dihydro-4, 7-ethano-2H-isoindole-l-carboxylate and 50 ml of anhydrous THF was cooled to 0°C.
  • Step 1-4 A solution of 0.02 g (O.032 mmol) of the resultant metal-free tetrabicyclo compound and 0.019 g (0.1 mmol) of cupric acetate monohydrate in a mixture of 30 ml of chloroform and 3 ml of methanol was stirred at room temperature for 3 hours. The reaction solution was washed with distilled water and a saturated salt solution, and was dried with anhydrous sodium sulfate. After the concentration of the solution, the concentrated product was recrystallized with chloroform/methanol to yield a tetrabicyclo copper complex (0.022 g, 100% yield).
  • Step 2-2 Benzyl acetoacetate (97 ml, 560 mmol) and acetic acid (81 ml) were fed into a reaction vessel. Then, a solution of sodium nitrite (37.8 g) in water (115 ml) was dropped into the mixture at 10 °C or lower. After the dropping, the mixture was stirred for 3 hours at room temperature.
  • Step 2-4 A reaction vessel was replaced with nitrogen, and 1-nitorpropane (8.93 ml, 100 mmol) and dry-THF (50 ml) were added.
  • Step 2-5) 4-hydroxy-3-nitrohexane (14.7 g, 100 mmol), acetic anhydride (14.8 ml, 157.3 mmol), chloroform (50 ml), and several drops of concentrated sulfuric acid were fed into a reaction vessel, and the mixture was stirred at room temperature for 10 hours. After the completion of the reaction, chloroform (50 ml) was added, and the whole was washed with water, a 5% aqueous solution of baking soda, and a saturated salt solution. The organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure to yield 4-acetoxy-3-nitrohexane (16.3 g, 86% yield) .
  • Step 2-6 After 4-acetoxy-3-nitrohexane (11.34 g, 60 mmol) had been added to a reaction vessel, the vessel was replaced with nitrogen, and dry-THF (150 ml) and ethyl isocyanoacetate (7.28 ml, 66 mmol) were added. Then, DBU (20.76 ml, 144 mmol) was slowly dropped while the vessel was cooled in an ice bath, and the whole was stirred at room temperature for 12 hours . After the completion of the reaction, 1 N hydrochloric acid was added, the whole was extracted with chloroform, and the extract was washed with water and a saturated salt solutio .
  • Step 2--7 Fed into a light-shielded reaction vessel equipped with a reflux condenser were 1.95 g (9.6 mmol) of ethyl-4, 7-dihydro-4, 7-ethano-2H-isoindole-l- carboxylate synthesized in Step 1-2, 100 ml of ethylene glycol, and 2.0 g of sodium hydroxide.
  • Step 2-8 Fed into a light-shielded reaction vessel equipped with a reflux condenser were ethyl 3, 4- diethylpyrrole-2-carboxylate obtained in Step 2-6 (2.056 g, 10.53 mmol), ethylene glycol (100 ml), and potassium hydroxide (3.5 g) . Then, the vessel was replaced with nitrogen and the mixture was stirred at 160°C for 2.5 hours. After that, the reaction solution cooled to room temperature was poured into ice water, the whole was extracted with ethyl acetate, and the extract was washed with an aqueous solution of baking soda, water, and a saturated salt solution. The organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure.
  • Step 2-9 Pd/C (0.5 g) and dry-THF (20 ml) were fed into a three-necked flask, and the mixture was replaced with hydrogen and stirred for 30 minutes.
  • Step 2-10 4, 7-dihydro-4, 7-ethano-2H-isoindole (0.12 g, 0.84 mmol) obtained in Step 2-7, 2, 5-bis (5-formyl-3- n-butyl-4-methyl-2-pyrroylmethyl) -3, 4-diethyl-lH- pyrrole (0.40 g, 0.84 mmol) obtained in Step 2-9, and chloroform (200 ml) were fed into a light-shielded reaction vessel, and the mixture was replaced with nitrogen.
  • TFA (10.0. ml) was added to the solution, and the mixture was stirred at 50°C for 18 hours. After the stirring, triethylamine (18.0 ml) was slowly dropped to neutralize the solution. After that, chloranil (0.21 g, 0.84 mmol) was added, and the mixture wasi stirred overnight. The resultant was quenched with an aqueous solution of sodium thiosulfate, and the organic layer was washed with water and a saturated salt solution and dried with anhydrous sodium sulfate. Zinc acetate was added to the dried product, and the whole was stirred at room temperature for 2 days.
  • Step 2-12 The resultant metal-free monobicyclo compound (0.041 g, 0.07 mmol) was fed into a reaction vessel, replaced with nitrogen, and dissolved into chloroform (25 ml). Cupric acetate monohydrate (0.028 g, 0.14 mmol) was added to the solution, and the whole was stirred' overnight . The reaction solution was poured into water, the whole was extracted with chloroform, and the extract was washed with a saturated salt solution. The organic layer was dried with anhydrous sodium sulfate and concentrated under reduced pressure to yield a monobicyclo copper complex (0.038 g, 87% yield) .
  • a silica sol e 0.8 g of dimethyldimethoxysilane and 0.2 g of tetramethoxysilane were completely dissolved into a mixed solvent composed of 48.8 g of ethanol and 49.5 g of 1-butanol. 0.67 g of distilled water and 0.05 g of formic acid were added to the solution, and the whole was stirred at room temperature for 48 hours to prepare a silica sol e.
  • Fig. IB shows the structure of a field effect transistor in this example.
  • a highly doped N type silicon substrate was provided as the gate electrode 1.
  • a silicon oxide film having a thickness of 5, 000 A obtained toy thermal oxidation of the surface layer of the silicon substrate was provided as the insulating layer 2.
  • the resin solution a was applied to the surface of the insulating layer by means of a spin coating method (at a number of revolutions of 5,000 rpm) .
  • the applied film was moved onto a hot plate and heated at 100°C for 5 minutes and 200°C for 20 minutes. Measurement with stylus-type step difference measuring device showed that the film had a thickness of 50 nm..
  • the film was provided as the A layer 3 (polysiloxane layer) .
  • the metal-free tetrabicyclo compound synthesized in Synthesis Example (1) in powder form was heated in a vacuum at 200°C to be transformed into a benzo compound, and was then formed into a film on the substrate by using a vacuum vapor deposition apparatus capable for which vacuum evacuation was performed by means of a diffusion pump
  • the film was provided as the B layer 6 (organic semiconductor layer) .
  • Conditions for producing a deposited film are as follows.
  • the degree of vacuum in the chamber of the evaporator was 1 x 10 ⁇ 6 torr
  • the temperature of the substrate was 220 °C
  • the deposition temperature was calculated from a quartz crystal micro-balance
  • the thickness and the deposition rate were 100 nm and 0.5 to 1.5 A/s, respectively.
  • the gold source electrode 4 and the drain electrode 5 were produced by using a mask.
  • Conditions for producing each of the electrodes are as follows.
  • the degree of vacuum in the chamber of the vapor deposition apparatus was 1 10 "6 torr, the temperature of the substrate was room temperature, and the thickness was 100 nm.
  • a field effect transistor having a channel length L of 50 ⁇ m and a channel width W of 3 mm was produced according to the above procedure.
  • the V d -I d and Vg-I d curves of the produced transistor were measured by using a Parameter Analyzer 4156C (trade name) manufactured by Agilent.
  • the mobility ⁇ (cm 2 /Vs) was calculated in accordance with the following equation (1) .
  • I d ⁇ (CiW/2L) x (V g - V th ) 2 (Eq. 1)
  • reference symbol Cj denotes the capacitance per unit area of the gate insulating film (F/cm 2 )
  • reference symbols W and L denote a channel width (mm) and a channel length ( ⁇ m) shown in the example, respectively
  • reference symbols I d , V g , and V th denote a drain current (A) , a gate voltage (V) , and a threshold voltage (V), respectively.
  • Example 2 A device was produced by the same operations as those of Example ' 1 except that, the metal-free tetrabicyclo body used in Example 1 was changed to the tetrabicyclo copper complex synthesized in Synthesis Example 1, and the device was evaluated for electrical characteristics. Ta le 1 shows the results .
  • Example 3 The same operations as those of Example 1 up to the production of the A layer were performed.
  • a 1- wt% solution of the metal-free tetrabicyclo body synthesized in Synthesis Example. 1 in chloroform was applied onto the substrate by means of a spin coating method (at a number of revolutions of 1,000 rpm) to form an applied film.
  • the substrate was heated at 220°C to form the B layer 6 composed of a benzo body.
  • the organic semiconductor layer had a thickness of 100 nm.
  • Gold was deposited onto the layer to form the source electrode 4 and the drain electrode 5.
  • a field effect transistor having a channel length L of 50 ⁇ m and a channel width of 3 mm was produced according to the above procedure, and was similarly evaluated for electrical characteristics. Table 1 shows the results.
  • CuK ⁇ X-ray diffraction measurement was performed for the produced transistor substrate under the following conditions.
  • Fig. 4 shows the results .
  • FIG. 2 shows the structure of a field effect transistor in this example.
  • a highly doped N type silicon substrate was provided as the gate electrode 1.
  • a silicon oxide film having a thickness of 5,000 A obtained by thermal oxidation of the surface layer of the silicon substrate was provided as the insulating layer 2.
  • the resin solution a was applied to the layer by the same operation as that of Example 1.
  • the film had a thickness of 50 nm.
  • the film was provided as the A layer 3.
  • Gold was deposited onto the layer by the same operation as that of Example 1 to form the source electrode 4 and the drain electrode 5.
  • a 1- wt% solution of the metal-free tetrabicyclo compound synthesized in Synthesis Example 1 in chloroform was applied onto the substrate by means of a spin coating method (at a number of revolutions of 1,000 rpm) to form an applied film.
  • the substrate was heated at 220°C to form the B layer 6 composed of a benzo compound.
  • the B layer had a thickness of 100 nm.
  • a field effect transistor having a channel length L of 50 ⁇ m and a -channel width W of 3 mm was produced according to the above procedure.
  • the transistor was evaluated for electrical characteristics in the same manner as in Example 1.
  • Table 1 shows the results.
  • Example 5 A device was produced by the same operations as those of Example 3 except that the metal-free tetrabicyclo compound used in Example 3 was changed to the tetrabicyclo copper complex, and the device was evaluated for electrical characteristics.
  • Table 1 and Fig. 3 show the results.
  • CuK ⁇ X- ray diffraction measurement was performed for the produced transistor substrate under the same conditions as those of Example 3.
  • Fig. 5 shows the results .
  • Example 1 The same operations as those of Example 4 were performed except that: the step of producing the A layer was omitted; the thickness of the silicon oxide film was changed to 3,000 A; the concentration of the solution of the metal-free tetrabicyclo compound was changed to 2 wt%; the substrate was sintered at 210 °C for 10 minutes; and the channel length L and the channel width W were changed to 25 ⁇ m and 0.25 mm, respectively. Table 1 shows the results. (Example 6) A device was produce ⁇ i by the same operations as those of Example 3 except that the metal-free tetrabicyclo compound used in Example 3 was changed to the metal-free monobicyclo compound synthesized in Synthesis Example 2, and the device was evaluated for electrical characteristics .
  • Table 1 shows the results.
  • CuK- ⁇ X-ray diffraction measurement was performed for the produced transistor substrate under the same conditions as those of Example 3.
  • Fig. 6 shows the results.
  • Example 7 A device was produced by the same operations as those of Example ' 3 except that . the metal-free tetrabicyclo compound used in Example . 3 was changed to the monobicyclo copper complex synthesized in Synthesis Example 2, and the device was evaluated for electrical characteristics .
  • Table 1 shows the results.
  • CuK ⁇ X-ray diffraction measurement was performed for the produced transistor substrate under the same conditions as those of Example 3.
  • Fig. 7 shows the results.
  • Example 8 The resin solution b was applied by the same operation as that of Example 1 to a highly doped N type silicon substrate having a silicon oxide film similar to that of Example 4.
  • the film had a thickness of 50 nm.
  • the film was provided as the A layer 3.
  • a l-wt% solution of the tetrabicyclo copper complex in chloroform was applied onto the substrate by means of a spin coating method (at a number of revolutions of 1,000 rpm) to form an applied film.
  • the substrate was heated at 220 °C to form the B layer 6 composed of a benzo compound.
  • the organic semiconductor layer had a thickness of 100 nm.
  • Gold was deposited onto the layer by the same operation as that of Example 1 to form the source electrode 4 and the drain electrode 5.
  • Table 1 shows the results.
  • Example 9 A device was produced by the same operations as those of Example 8 except that an applied film having a thickness of 50 nm was formed by using the resin solution c and was provided as the A layer 3, and the device was evaluated for electrical characteristics.
  • Table 1 shows the results.
  • Example 10 A device was produced by the same operations as those of Example 8 except that an applied film having a thickness of 50 nm was formed by using the silica sol d and was provided as the A layer 3, and the device was evaluated for electrical characteristics. Table 1 shows the results.
  • Example 11 A device was produced by the same operations as those of Example 8 except that an applied frilm having a thickness of 50 nm was formed by using trie silica sol e and was provided as the A layer 3, and the device was evaluated for electrical characteristics . Table 1 shows the results.
  • Example 12 Fig. 8 shows the structure of a field effect transistor in this example.
  • a silver nanoparticle paste manufactured by Nippon Paint Co., Ltd., Fine Sphere SVE102
  • the resin solution b was applied to the surface of the insulating layer by means of a spin coating method (at a number of revolutions of 3,000 rpm) .
  • the applied film was heated in an oven with internal air circulation at 180°C for 20 minutes.
  • the film had a thickness of 60 nm.
  • the film was provided as the A layer 3.
  • a l-wt% solution of the metal-free tetrabicyclo compound synthesized in Synthesis Example 1 in chloroform was applied onto the substrate by means of a spin coating method (at a number of revolutions of 1,000 rpm) to form an applied film. Furthermore, the substrate was heated at 220°C to form the B layer 6 composed of a benzo body. The organic semiconductor layer had a thickness of 100 nm. Gold was deposited onto the layer by the same operation as that of Example 1 to form the source electrode 4 and the drain electrode 5. Table 1 shows the results.
  • Example 13 A device was produced by the same operations as those of Example 11 except that the metal- free tetrabicyclo compound used in Example 12 was changed to the tetrabicyclo copper complex, and the device was evaluated for electrical characteristi cs .
  • Table 1 shows the results.
  • CuK ⁇ X-n-ray diffraction measurement was performed for the produced transistor substrate under the same conditions as those of Example 3.
  • Fig. 9 shows the results .
  • Example 14 A device was produced by the same operations as those of Example 13 except that heating ti-me to form the B layer 6 from tetrabicyclo copper com-plex was changed to 1, 5 and 10 minutes, and the device was evaluated for electrical characteristics.
  • Fig. 10 shows the results.
  • Example 15 A device was produced by the same operations as those of Example 5 except that heating to form the B layer 6 from tetrabicyclo copper complex was conducted in an oven with internal air circulation at 180°C and heating time was changed to 30, 60 and 90 minutes, and the device was evaluated for electrical characteristics. ' Fig. 11 shows the resultes. (Comparative Example 2) those of Example 14 except that the step of producing the A layer 3, and the device was evaluated for electrical characteristics. Fig. 10 shows the results . (Comparative Example 3) A device was produced by the same o erations as those of Example 15 except that the step of producing the A layer 3, and the device was evaluated for electrical characteristics. Fig. 10 shows the 10 results .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)

Abstract

Il est fourni un transistor à effet de champ comportant une couche de semiconducteur organique incluant : une couche de semiconducteur organique contenant au moins de la porphyrine et une couche composée au moins d'un composé de polysiloxane, la couche étant stratifiée sur la couche de semiconducteur organique de façon à être en contact rapproché avec la couche de semiconducteur organique. Il en résulte qu'il peut être fourni un transistor à effet de champ qui permet que soit formée une couche de semiconducteur organique présentant une caractéristique cristalline élevée et une orientation élevée et qui affiche une mobilité élevée.
PCT/JP2005/004586 2004-03-10 2005-03-09 Transistor à effet de champ, procédé de fabrication de celui-ci est procédé de fabrication d'un élément stratifié WO2005086254A1 (fr)

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US7435989B2 (en) * 2005-09-06 2008-10-14 Canon Kabushiki Kaisha Semiconductor device with layer containing polysiloxane compound
US7695999B2 (en) * 2005-09-06 2010-04-13 Canon Kabushiki Kaisha Production method of semiconductor device
CN102110776A (zh) * 2010-12-03 2011-06-29 中国科学院化学研究所 一种高性能有机场效应晶体管及其制备方法
US8134144B2 (en) * 2005-12-23 2012-03-13 Xerox Corporation Thin-film transistor
US8741468B2 (en) 2006-03-13 2014-06-03 Nec Corporation Film-packaged electric device

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JP2005079203A (ja) * 2003-08-28 2005-03-24 Canon Inc 電界効果型トランジスタおよびその製造方法
JP4401826B2 (ja) * 2004-03-10 2010-01-20 キヤノン株式会社 電界効果型トランジスタおよびその製造方法
JP4401836B2 (ja) * 2004-03-24 2010-01-20 キヤノン株式会社 電界効果型トランジスタおよびその製造方法
US7511296B2 (en) 2005-03-25 2009-03-31 Canon Kabushiki Kaisha Organic semiconductor device, field-effect transistor, and their manufacturing methods
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US7397086B2 (en) * 2005-12-23 2008-07-08 Xerox Corporation Top-gate thin-film transistor
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US8741468B2 (en) 2006-03-13 2014-06-03 Nec Corporation Film-packaged electric device
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US20070012914A1 (en) 2007-01-18

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